Container closure

ABSTRACT

Closure ( 1 ) for a container, in particular for pourable or flowable products, has a closure head ( 2 ), a circumferential face ( 3 ) which is connected at least partially to the closure head ( 2 ), and means ( 6 ) which interact with the container in such a way that the discharge opening of the container can be closed by the closure ( 1 ), with the result that the closure ( 1 ) has means ( 4 ) for fixing a plurality of portion containers ( 7 ) of in each case less than 50 ml filling volume to the closure ( 1 ). The portion containers ( 7 ) are filled with at least one additive, such as fragrances, dyes or surfactants, that can be mixed selectively with the pourable or flowable product located in the container.

The invention relates to a closure for a container, in particular for a bottle or a can for pourable and/or free-flowing consumer products, such as, for example from the group of pharmaceuticals, cosmetics, agricultural auxiliaries, building materials, dyes, textile detergents, dishwasher detergents, adhesives or foodstuffs.

PRIOR ART

There has long been a need for individualizing products specifically for the consumer or allowing products to be individualized to a certain degree by the consumer. A particularly suitable medium for the individualization of a product is its packaging, as this forms the direct interface between consumer and product.

Accordingly, it is desirable to directly link agents for the individualization or additional functionalization of a product with the product packaging.

Particularly in the sector of perfuming of products, such as for example cleaning agents, detergents and the like, it is still usual nowadays to sell the total sales unit with a defined odor. However, the consumer often wishes that a cleaning product release a different odor for different fields of application. Thus, for example it is desirable that a toilet cleaning agent release a more intensive odor than does a household cleaner, intensive odors often being perceived as rather annoying in the living area. Consequently, up to now it has been necessary to use a great number of special cleaners with the corresponding odors, although each of the active cleaning preparations are identical or at least very similar.

Moreover, with very aggressive cleaning preparations, there is the problem that the aggressive cleaning components also destroy the fragrances contained in the preparation, such that they only exhibit a short shelf life.

In addition to the preparation of individually perfumed products, there is a further requirement for a product packaging to be designed in such a way that the odor of the product comprised in the packaging be olfactively perceptible.

Finally, packaging also tends to be increasingly further functionalized, in that odoriferous substances are located on the packaging and release a defined odor into the surroundings of the packaging, thus assuming the additional role of a room freshener.

From WO2004/084660 it is known to locate odoriferous substances in a closing cap of a container. The container closure has a cavity that contains a fragrance emitting material and is sealed with a film that can be removed to emit the fragrance into a room from the container closure. The disadvantage of this solution is the comparatively large and thereby somewhat unwieldy shape of this closure for the consumer. As a result of the fact that the internal volume of the closure is almost completed filled with a fragrance, there is hardly any more dosing volume available, such that the closure generally cannot be used for metering, as can for example closures of rinsing agents or floor cleaners. The required increased size in comparison with that of normal closures also increases the storage requirements for this type of container and inevitably leads to increased logistic costs.

CA983437 discloses a container for medical uses where it is necessary for the patient to take prescribed dosages of a tablet or capsule in combination with a liquid. According to CA983437 a container disposes of a means for retaining the individual doses on the external wall of the container. They are recesses in the external wall, in which the individual doses can be inserted or stored. The doses located in the recesses are then fixed with an adhesive tape in the recesses. To remove a dose, the adhesive tape can then be lifted up and removed, such that a dose is released and can be removed from the recess in the external wall of the container.

This solution has the disadvantage that the production of a suitable container is expensive and technically complicated. Moreover, extensive surfaces are required thus significantly restricting the room for advertising and/or labelling. Consequently, the overall esthetic impression of the container is markedly negatively affected. A further disadvantage of this solution is that no pasty or preparations in gel form can be metered and removed.

OBJECT OF THE INVENTION

Accordingly, the object of the present invention is to create a closure that enables the provision of preferably a plurality of individually packaged portionable product units in a simple and easily utilizable manner on a container closure and which enables individual product units to be removed without a complete separation of the closure from the container.

The object is achieved according to the features of Claim 1.

A significant advantage of the closure according to the invention is that it can be manufactured very cheaply. Because constructive design modifications are not required on the container, the provision of the product units on the closure is much more favorable from the viewpoint of production and economics, as a container closure is usually injection molded, such that the specifications in regard to precision and geometric complexity can be usually met and technically mastered. Today, the blow molding process is frequently used for containers and allows lightweight bottles in particular to be made cheaply for dishwashing detergents and cleaning agents, for example. However, complex geometries and particularly production tolerances, as are needed for a product unit to be fixed directly on the container, are technically and/or economically not achievable.

Further, the inventive solution can be easily adapted to existing closures.

Because the defined active substances (fragrance, enzymes, bleaches etc.) in a preparation can be spatially separated by means of the invention and they can be disposed in portions in the container closure, the product in the container is very easily made up.

The contents of the portion containers can consist of one or more identical or different products or additives such as for example fragrances, cleaning substances, dyes, enzymes, hygroscopic substances and the like.

Thus for example, it would be possible to locate substances with different fragrances in the portion containers in order to provide the contents of the container with different scents. Thus, for example when a cleaning liquid with a neutral odor is diluted with water to make a mopping preparation, then a different fragrance can be metered into each mopping water preparation from a portion container. Firstly this prevents the olfactory adaptation to a defined fragrance, secondly a fragrance can be selected for the requirements of each specific application area (toilets, living room, kitchen). The use of a plurality of specifically perfumed cleaning substances is no longer required for this, and consequently is also environmentally desirable and resource-friendly.

The individually packaged portionable additive product units are fixed by means of a suitable form locked, friction locked or material joined connection on the closure. Preferred types of connections are snap-in connections, press-fitted assemblies, fused joints, adhesive joints, Velcro® fasteners.

According to a particular embodiment of the invention, the individually packaged portionable product units possess a closure. This can be formed on the product unit for example by a twistable lid or a weakened line, a stopper, a sealing film.

The closure and/or the opening of the container can optionally possess dosing and removal aids, such as an aerosol valve, a spout, a spray cap, a spray nozzle, a metering device, a metering cap, a metering mouth piece or a dripper.

In the context of the present application, “additive” is understood to mean a substance or mixture of substances, which on mixing with the product located in the container, suitably achieves or influences, especially improves, produces, accentuates, attenuates a property of the product, accelerates or decelerates a temporal process, initiates, inhibits or catalyzes a reaction. Furthermore, “additive” should also be understood to mean a substance or a mixture of substances, which suitably achieves or influences a property of the container, especially fragrance release and/or active substance release, adsorption or absorption on or in the container.

The additive can include for example one or more substances from the group of the fragrances, bleaching agents, cleaning substances, solvents, surfactants, dyes, enzymes, hygroscopic substances, flame retardants, hardeners, leveling agents, wetting agents, dispersants, foaming agents, defoamers, exhausters, corrosion protectants, biocides, water softeners, preservatives, emulsifiers, stabilizers, vitamins, minerals and the like.

Polymeric Carrier Material

According to a preferred embodiment of the invention, the active additive substances are bound to or in a polymeric carrier material. Fragrances are particularly preferably bound in or to a polymeric carrier material.

In general, all polymers or polymer mixtures that meet the criteria cited above in regard to the melting temperature or softening temperature are suitable for the fragrance-containing particles. In the context of the present application, preferred fragrance releasing systems are characterized in that the polymeric carrier material comprises at least one substance from the group comprising ethylene/vinyl acetate copolymers, polyethylenes of low or high density (LDPE, HOPE) or mixtures thereof, polypropylene, polyethylene/polypropylene copolymers, polyether/polyamide block copolymers, styrene/butadiene (block) copolymers, styrene/isoprene (block) copolymers, styrene/ethylene/butene copolymers, acrylonitrile/butadiene/styrene copolymers, acrylonitrile/butadiene copolymers, polyether esters, polyisobutene, polyisoprene, ethylene/ethyl acrylate copolymers, polyamides, polycarbonate, polyesters, polyacrylonitrile, polymethyl methacrylate, polyurethanes polyvinyl alcohols.

Polyethylene (PE) is a collective name for polymers belonging to the polyolefins containing groups of the type

CH₂—CH₂

as the characteristic basic unit of the polymer chain. Polyethylenes are generally manufactured by the polymerization of ethylene according to two fundamentally different methods, the high pressure and the low pressure processes. The resulting products are often referred to as high pressure polyethylenes and low pressure polyethylenes respectively; they differ principally in regard to their degree of branching and consequently in their crystallinity and density. Both processes can be carried out as a solution polymerization, emulsion polymerization or gas phase polymerization.

The high pressure process produces polyethylenes with low density (ca. 0.915-0.935 g/cm³) and crystallinities of ca. 40-50%, which are called LDPE types (low density polyethylene). Products with higher molecular weight and as a result improved tensile and elongation properties, are given the abbreviation HMW-LDPE (HMW=high molecular weight). The pronounced degree of branching of the polyethylenes produced in the high pressure process can be reduced by copolymerization of the ethylene with longer chain olefins, particularly butene and octene; the copolymers have the abbreviation LLD-PE (linear low density polyethylene).

The polyethylene macromolecules from the low pressure process are largely linear and unbranched. These polyethylenes, abbreviated HDPE (from the English, high density polyethylene), have crystallinities of 60-80% and a density from ca. 0.940-0.965 g/cm³. They are offered as products with high or ultra-high molecular weight (ca. 200 000-5 000 000 g/mol and 3 000 000-6 000 000 g/mol) under the abbreviation HD-HMW-PE and UHMW-HD-PE. Medium density products (MDPE) from blends of polyethylenes of low and high density are also commercially available. Linear polyethylenes with densities <0.918 g/cm³ (VLD-PE, from the English very low density polyethylene) are only slowly gaining market importance.

Polyethylenes have a very low water vapor permeability; the diffusion of gases as well as aromas and ethereal substances through polyethylene is relatively high. The mechanical properties are strongly dependent on the molecular size and structure of the polyethylene. Generally, crystallinity and density of polyethylenes increase with decreasing degrees of branching and with shortened side chains. Shear modulus, hardness, yield stress and melting point increase with the density; impact resistance, transparency, swellability and solubility decrease. With increasing molecular weight, tensile strength, elongation, shock resistance, impact resistance and creep resistance increase for polyethylenes of the same density. Depending on the procedure in the polymerization, it is possible to obtain products having paraffin wax-like properties (MR about 2000) and products of maximum toughness (MR above 1 million).

The polyethylene types can be processed by all typical methods used for thermoplastics.

Polypropylene (PP) is the name for thermoplastic polymers of propylene with the general formula:

—(CH₂—CH[CH₃])_(n)—

The basis of polypropylene production was the development by Natta of the process for the stereospecific polymerization of propylene in the gas phase or in suspension. This is initiated by Ziegler-Natta catalysts, but to an increasing degree also by metallocene catalysts, and leads either to highly crystalline isotactic or to less crystalline syndiotactic or to amorphous atactic polypropylenes.

Polypropylene features high hardness, resilience, stiffness and heat resistance. It is possible to briefly heat objects made of propylene even up to 140° C. At temperatures below 0° C., a certain embrittlement of the polypropylenes occurs, but can be shifted to substantially lower temperature ranges by copolymerization of the propylene with ethylene (EPM, EPDM). Generally, the impact strength of polypropylene can be improved by modification with elastomers. As in the case of all polyolefins, the chemical resistance is good. An improvement in the mechanical properties of the polypropylenes is achieved by reinforcement with talc, chalk, wood flour or glass fibers. Polypropylenes are oxidation- and light-sensitive to an even greater degree than PE, which is why it is necessary to add stabilizers (antioxidants, light stabilizers, UV absorbers).

Polyether is an umbrella term in the field of macromolecular chemistry for polymers whose organic repeating units are linked together through ether functionalities (C—O—C). According to this definition, a multitude of structurally very different polymers belongs to the polyethers, for example the polyalkylene glycols (polyethylene glycols, polypropylene glycols and polyepichlorohydrins) as polymers of 1,2-epoxides, epoxy resins, polytetrahydrofurans (polytetramethylene glycols), polyoxetanes, polyphenylene ethers (see polyaryl ethers) or polyether ether ketones (see polyether ketones). The polyethers do not include polymers having pendent ether groups, such as inter alia the cellulose ethers, starch ethers and vinyl ether polymers.

The group of the polyethers also includes functionalized polyethers, i.e. compounds having a polyether structure which also bear, attached pendent to their main chains, other functional groups, for example carboxyl, epoxy, allyl or amino groups, etc. Block copolymers of polyethers and polyamides (known as polyether amides or polyether block amides, PEBA) have a variety of possible uses.

Polyamides (PA) refer to polymers whose basic units are linked together through amide bonds (—NH—CO—). Naturally occurring polyamides are peptides, polypeptides and proteins (for example albumin, wool, silk). Apart from a few exceptions, the synthetic polyamides are thermoplastic, catenated polymers, some of which have gained great industrial significance as synthetic fibers and materials. According to the chemical structure, what are known as the homopolyamides can be divided into two groups, the amino carboxylic acid types (AC) and the diamine-dicarboxylic acid types (AA-CC; A denotes amino groups and C carboxyl groups). The former are prepared from only a single monomer by, for example, polycondensation of an ω-amino carboxylic acid (1) (polyamino acids) or by ring-opening polymerization of cyclic amides (lactams) (2).

In addition to the homopolyamides, some copolyamides have also gained significance. It is customary to qualitatively and quantitatively specify the composition, for example PA 66/6 (80:20) for polyamides prepared from 1,6-hexanediamine, adipic acid and ε-caprolactam in a molar ratio of 80:80:20. Owing to their special properties, polyamides that contain exclusively aromatic groups (for example those made from p-phenylenediamine and terephthalic acid) are defined by the generic name of aramids or polyaramids (for example Nomex®).

The most frequently used polyamide types (in particular PA 6 and PA 66) consist of unbranched chains with average molar weights of 15 000 to 50 000 g/mol. They are semi-crystalline in the solid state and have degrees of crystallization of 30-60%. An exception is that of polyamides made from units having side chains, or copolyamides made from highly differing components, and which are substantially amorphous. In contrast to the generally milky, opaque semi-crystalline polyamides, these are almost glass-clear. The softening temperatures of the most commonly used homopolyamides are between 200 and 260° C. (PA 6: 215-220° C., PA 66: 255-260° C.).

Polyesters is the collective term for polymers whose basic units are held together by ester bonds (—CO—O—). According to their chemical structure, what are known as the homopolyesters can be divided into two groups, the hydroxycarboxylic acid types (AB polyesters) and the dihydroxydicarboxylic acid types (AA-BB polyesters). The former are prepared from only a single monomer by, for example, polycondensation of an ω-hydroxycarboxylic acid 1 or by ring-opening polymerization of cyclic esters (lactones) 2.

Branched and crosslinked polyesters are obtained in the polycondensation of tri- or polyhydric alcohols with polyfunctional carboxylic acids. The polycarbonates (polyesters of carbonic acid) are also generally included under polyesters. AB-type polyesters (I) include polyglycolic acids, polylactic acids, polyhydroxybutyric acid [poly(3-hydroxybutyric acid)], poly(ε-caprolactone)s and polyhydroxybenzoic acids.

Purely aliphatic AA-BB-type polyesters (II) are polycondensates of aliphatic diols and dicarboxylic acids which can be used, inter alia, as products having terminal hydroxyl groups (as polydiols) for the preparation of polyester polyurethanes [for example polytetramethylene adipate]. In quantitative terms, the greatest industrial significance belongs to AA-BB-type polyesters made from aliphatic diols and aromatic dicarboxylic acids, in particular the polyalkylene terephthalates, with polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and poly(1,4-cyclohexane-dimethylene terephthalate)s (PCDT) as the most important representatives. The properties of these types of polyesters can be varied widely by also using other aromatic dicarboxylic acids (e.g. isophthalic acid) or by using diol mixtures in the polycondensation, and they can be adapted to different fields of use.

Purely aromatic polyesters are the polyarylates, which include poly(4-hydroxybenzoic acid). In addition to the saturated polyesters mentioned previously, it is also possible to prepare unsaturated polyesters from unsaturated dicarboxylic acids; unsaturated polyesters have gained industrial significance as polyester resins, in particular as unsaturated polyester resins (UP resins).

Polyesters are generally thermoplastics. Products based on aromatic dicarboxylic acids have exceptional materials properties. The purely aromatic polyarylates are characterized by high thermal stability.

Polyurethanes (PUR) denote polymers in whose macromolecules the repeating units are joined by urethane moieties —NH—CO—O—. Polyurethanes are obtained generally by polyaddition of dihydric or higher polyhydric alcohols to isocyanates.

Depending on the selection and stoichiometric ratio of the starting materials, polyurethanes are thus formed, which have very different mechanical properties and can be used as constituents of adhesives and coatings (polyurethane resins), as ionomers, as a thermoplastic material for bearing parts, castors, tires, rollers, and as more or less hard elastomers in fiber form (elastomeric fibers, abbreviated to PUE for these Elastan or Spandex fibers) or as polyether or polyester urethane rubber (EU and AU respectively).

Polyurethane foams are formed from the polyaddition in the presence of water and/or carboxylic acids because these react with the isocyanates with the elimination of carbon dioxide that acts as a blowing and a foaming-agent. The use of polyalkylene glycol ethers as diols and water as a reaction component leads to flexible polyurethane foams; the use of polyols and propellant gases from CFCs (particularly R11) affords rigid polyurethane foams and structural or integral foams. Examples of auxiliaries additionally required here are catalysts, emulsifiers, foam stabilizers (particularly polysiloxane-polyether copolymers), pigments, aging inhibitors and flame retardants. For the production of objects made of polyurethane foam, even those having a complicated shape, reaction injection molding, known as the RIM technique, was developed in the 1970s. The RIM process is based on rapid metering and mixing of the components, injection of the reactive mixture into the mold and rapid curing; the cycle time being only a few minutes. Objects including automotive bodywork parts, shoe soles, window profiles and television casings are obtained by the RIM technique.

Polyvinyl alcohols (PVAL, occasionally also PVOH) is the term for polymers of the general structure

which also contain small proportions (approx. 2%) of structural units of the type

Commercial polyvinyl alcohols are supplied as white-yellowish powders or granules having degrees of polymerization in the range from approx. 100 to 2500 (molecular weights of approx. 4000 to 100 000 g/mol). The polyvinyl alcohols are characterized by the manufacturers by specifying the degree of polymerization of the starting polymer, the degree of hydrolysis, the hydrolysis number and the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); they are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as being toxicologically harmless and are at least partly biodegradable. The solubility in water can be reduced by after treatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The coatings made of polyvinyl alcohol are substantially impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

The materials which are used for the container are preferably polyvinyl alcohols of a defined molecular weight range, preference being given in accordance with the invention to the water-soluble or water-dispersible container comprising a polyvinyl alcohol whose molecular weight is in the range of from 10 000 to 100 000 gmol⁻¹, preferably of from 11 000 to 90 000 gmol⁻¹, more preferably of from 12 000 to 80 000 gmol⁻¹ and in particular of from 13 000 to 70 000 gmol⁻¹.

In a particularly preferred embodiment of the present invention, the polymeric carrier material of the particles consists at least partially of ethylene/vinyl acetate copolymer. The present application therefore further preferably provides a fragrance release system, characterized in that the polymeric carrier material contains at least 10% by weight, preferably at least 30% by weight, more preferably at least 70% by weight, of ethylene/vinyl acetate copolymer, and is preferably produced fully from ethylene/vinyl acetate copolymer.

Ethylene/vinyl acetate copolymers is the term for copolymers made from ethylene and vinyl acetate. This polymer is in principle prepared in a process comparable to the preparation of polyethylene of low density (LDPE; low-density polyethylene). With an increasing proportion of vinyl acetate, the crystallinity of the polyethylene is disrupted, thus lowering the melting and softening points and the hardness of the resulting products. The vinyl acetate additionally renders the copolymer more polar and thus improves its adhesion to polar substrates.

The above-described ethylene/vinyl acetate copolymers are commercially widely available, for example under the trademark Elvax® (Dupont). Particularly suitable polyvinyl alcohols in the context of the present invention are, for example, Elvax® 265, Elvax® 240, Elvax® 205 W, Elvax® 200 W and Elvax® 360.

Some particularly suitable copolymers and their physical properties can be found in the following Table:

Wt. % vinyl acetate Product Name (based on total wt.) Melting point Elvax ® 40W 40 47° C. Elvax ® 150 33 63° C. Elvax ® 265 28 75° C. Elvax ® 240 28 74° C. Elvax ® 205 W 28 72° C. Elvax ® 200 W 28 71° C. Elvax ® 360 25 78° C. Elvax ® 460 18 88° C. Elvax ® 660 12 96° C. Elvax ® 760 9 100° C. 

In the context of the present invention, especially in the field of fragrancing interiors, particular preference is given to fragrance release systems, in which ethylene/vinyl acetate copolymer is used as the polymeric carrier material, the copolymer comprising from 5 to 50% by weight of vinyl acetate, preferably from 10 to 40% by weight of vinyl acetate and in particular from 20 to 30% by weight of vinyl acetate, based in each case on the total weight of the copolymer.

Inventive fragrance release systems comprise the polymeric carrier materials in the form of particles. The three-dimensional shape of these particles is restricted solely by the technical possibilities for their production. Possible three-dimensional shapes are all embodiments that can be handled viably, i.e., for example, cubes, cuboids and corresponding three-dimensional elements having flat lateral surfaces, and also in particular cylindrical embodiments with circular or oval cross section. This last embodiment includes tablet-shaped particles up to compact cylinder sections having a ratio of height to diameter greater than 1. Further possible three-dimensional shapes are spheres, hemispheres or “stretched spheres” in the form of ellipsoidal capsules, as are regular polyhedra, for example tetrahedra, hexahedra, octahedra, dodecahedra, icosahedra. Also conceivable are star-shaped embodiments with three, four, five, six or more points or fully irregular bodies that can be configured, for example, in a motif. Suitable motifs, depending upon the field of use of the inventive compositions are, for example, animal figures such as dogs, horses or birds, floral motifs or the illustration of fruits. However, the motif-type embodiment may also relate to inanimate objects such as vehicles, tools, household objects or clothing. The surface of the solid particles may have unevenness depending upon the type of production process selected and/or a selected coating. Owing to the numerous possible embodiments of the particles, the inventive compositions are notable for advantages not only in their production. Owing to the numerous embodiment forms, the fragrance-containing particles are additionally clearly perceptible visually to the consumer and enable, by the selective spatial configuration of these particles, a visualization, particularly advantageous for product acceptance, of the fragrances present in the inventive compositions or further active substances optionally present in these compositions. For instance, the visually perceptible multiphase form of these compositions may illustrate, for example, the differing function of individual active substances (for example cleaning and additional functions such as glass protection, silver protection, etc.).

In the context of the present application, particles have a solid consistency at room temperature, i.e. are dimensionally stable and not free-flowing. Preferred particles have an average diameter of 0.5 to 20 mm, preferably of 1 to 10 mm and in particular of 3 to 6 mm.

The polymeric carrier materials can be converted into the above-described particles by all processes known to those skilled in the art for the processing of these substances. Preference is given in the context of the present invention to extrusion, injection molding and spraying to afford polymer granules.

Fragrances

In the context of the present invention, suitable perfume oils or fragrances include individual odoriferous compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Perfume compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tent.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; the ketones include, for example, the ionones, α-isomethyl ionone and methyl cedryl ketone; the alcohols include anethol, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol and the hydrocarbons include, above all, the terpenes, such as limonene and pinene. However, mixtures of various odoriferous substances, which together produce an attractive fragrant note, are preferably used. Perfume oils such as these may also contain natural perfume mixtures obtainable from vegetal sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are muscatel oil, oil of sage, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetivert oil, olibanum oil, galbanum oil and laudanum oil and orange blossom oil, neroli oil, orange peel oil and sandalwood oil.

The general description of the employable perfumes (see above) generally illustrates the different substance classes of perfumes. The volatility of a perfume is crucial for its perceptibility, whereby in addition to the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays a role. Thus, the majority of odoriferous substances have molecular weights up to 200 daltons, and molecular weights of 300 daltons and above are quite an exception. Due to the different volatilities of perfumes, the smell of a perfume or fragrance composed of a plurality of odoriferous substances changes during evaporation, the impressions of odor being subdivided into the “top note”, “middle note” or “body” and “end note” or “dry out”. As the perception of smell also depends to a large extent on the intensity of the odor, the top note of a perfume or fragrance consists not solely of highly volatile compounds, whereas the end note consists to a large extent of less volatile, i.e. tenacious odoriferous substances. In the composition of perfumes, higher volatile odoriferous substances can be bound, for example onto particular fixatives, whereby their rapid evaporation is impeded. In the following subdivision of perfumes into “more volatile” or “tenacious” perfumes, nothing is mentioned about the odor impression and further, whether the relevant perfume is perceived as the top note or body note.

An appropriate selection of the mentioned fragrances and perfume oils for the inventive composition can have an influence on both the product odor, directly on opening the new composition as well as on the end-use fragrance, for example when used in a machine dishwasher. These perceived fragrances may of course be the same but they may also be different. It is advantageous to use more firmly adhering odorants for the latter perceived odor, while more volatile odorants can also be used to fragrance the product. Exemplary tenacious odorous substances that can be used in the context of the present invention are the ethereal oils such as angelica root oil, aniseed oil, arnica flowers oil, basil oil, bay oil, bergamot oil, champax blossom oil, silver fir oil, silver fir cone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, geranium oil, ginger grass oil, guaiacum wood oil, Indian wood oil, helichrysum oil, ho oil, ginger oil, iris oil, cajuput oil, sweet flag oil, camomile oil, camphor oil, Canoga oil, cardamom oil, cassia oil, Scotch fir oil, copaiba balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemon grass oil, limette oil, mandarin oil, melissa oil, amber seed oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, orange oil, origanum oil, Palma Rosa oil, patchouli oil, Peru balsam oil, petit grain oil, pepper oil, peppermint oil, pimento oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery seed oil, lavender spike oil, Japanese anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, ysop oil, cinnamon oil, cinnamon leaf oil, citronella oil, citrus oil and cypress oil. However, in the context of the present invention, the higher boiling or solid odoriferous substances of natural or synthetic origin can be used as tenacious odoriferous substances or mixtures thereof, namely fragrances. These compounds include the following compounds and their mixtures: ambrettolide, α-amyl cinnamaldehyde, anethol, anisaldehyde, anis alcohol, anisole, methyl anthranilate, acetophenone, benzyl acetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valeriate, borneol, bornyl acetate, α-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, methyl heptyne carboxylate, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, irone, isoeugenol, isoeugenol methyl ether, isosafrol, jasmone, camphor, carvacrol, carvone, p-cresol methyl ether, coumarone, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilic acid methyl ester, p-methyl acetophenone, methyl chavicol, p-methyl quinoline, methyl β-naphthyl ketone, methyl n-nonyl acetaldehyde, methyl n-nonyl ketone, muscone, β-naphthol ethyl ether, β-naphthol methyl ether, nerd, nitrobenzene, n-nonyl aldehyde, nonyl alcohol, n-octyl aldehyde, p-oxyacetophenone, pentadecanolide, β-phenylethyl alcohol, phenyl acetaldehyde dimethyl acetal, phenylacetic acid, pulegone, safrol, isoamyl salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, santalol, scatol, terpineol, thymine, thymol, γ-undecalactone, vanillin, veratrum aldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, ethyl cinnamate, benzyl cinnamate. The readily volatile odoriferous substances particularly include the low boiling odoriferous substances of natural or synthetic origin that can be used alone or in mixtures. Exemplary readily volatile odoriferous substances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linalyl acetate and linalyl propionate, menthol, menthone, methyl n-heptenone, phellandrene, phenyl acetaldehyde, terpinyl acetate, citral, citronellal.

The plastics particles are preferably loaded with the selected fragrance at a temperature of 15 to 30° C., preferably 20 to 25° C. To this end, the appropriate amount of the fragrance is added to the particles and blended together. In all cases, however, the temperature should be below the melting or decomposition temperature of the plastic and also below the flashpoint of the perfume oil. The fragrance is absorbed by the polymeric carrier material or by further perfume carrier materials present in the particles primarily by adhesion, diffusion and/or capillary forces, and may cause the particles to swell slightly in the course of this operation.

Further Active Substances

As mentioned above, inventive compositions may comprise, apart from the constituents needed for fragrancing and deodorization, further active substances. From the compositions which serve exclusively for fragrancing, it is accordingly possible to differentiate further product groups that comprise further preferred substances in addition to the aforementioned inventive constituents.

Dyes

A first of these optionally usable preferred substances is the dyes. Generally, all dyes are suitable, which are known to the person skilled in the art as being suitable for coloring plastics and which are soluble in perfume oils. The dye is preferably selected according to the fragrance used; for example, particles having a lemon fragrance preferably have a yellow color, whereas a green color would be preferred for particles having an apple or herb fragrance. Preferred dyes have a high storage stability and are insensitive toward the remaining ingredients of the compositions and to light. When the inventive compositions are used in connection with textile cleaning or dishwashing, the dyes used should not have any marked substantivity toward textile fibers, glass, plastic ware or ceramics, in order not to stain them.

Suitable dyes and dye mixtures are commercially available under various trade names and are supplied by firms including BASF AG, Ludwigshafen, Bayer AG, Leverkusen, Clariant GmbH, DyStar Textilfarben GmbH & Co. Deutschland KG, Les Colorants Wackherr SA and Ciba Specialty Chemicals. The suitable fat-soluble dyes and dye mixtures include, for example, Solvent Blue 35, Solvent Green 7, Solvent Orange 1 (Orange au Gras-W-2201), Sandoplast Blau 2B, Fettgelb 3G, Iragon® Red SRE 122, Iragon® Green SGR 3, Solvent Yellow 33 and Solvent Yellow 16, although other dyes may also be present.

In a preferred embodiment, the dye, in addition to its esthetic effect, additionally has an indicator function. This indicates to the consumer the actual consumption level of the deodorant, so that he/she obtains, in addition to the absence of fragrance impression which may, for example, be based on an accustoming effect on the part of the user, a further reliable indication as to when the deodorant should be replaced by a new one.

The indicator effect may be achieved in various ways: one way is to use a dye, which escapes from the particles in the course of the period of use. This may be caused, for example, by the ingredients present in the dishwasher detergent. To this end, a dye has to be used, which adheres well to the particles and only slowly diffuses out of them, in order to ensure that the discoloration is not complete too early, i.e. when the fragrance has not yet been consumed. Another way is that a color change is caused by a chemical reaction or thermal decomposition.

Antimicrobials, Germicides, Fungicides

Further preferred constituents of the inventive compositions are substances such as antimicrobials, germicides, fungicides, antioxidants or corrosion inhibitors, with the aid of which, additional uses, for example disinfection or corrosion protection, can be realized.

The compositions according to the invention may contain antimicrobials to control microorganisms. Depending on the antimicrobial spectrum and the action mechanism, antimicrobial agents are classified as bacteriostatic agents and bactericides, fungistatic agents and fungicides, etc. important substances from these groups are for example benzalkonium chlorides, alkylaryl sulfonates, halophenols and phenol mercury acetate.

Antioxidants

The compositions can comprise antioxidants in order to prevent undesirable changes caused by oxygen and other oxidative processes to the compositions according to the invention or the treated fabric surfaces. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

When the inventive compositions are used in machine dishwashers, these compositions may comprise corrosion inhibitors to protect the tableware or the machine, silver protection agents being particularly important in machine dishwashers. Substances known from the prior art can be incorporated. Above all, silver protectors selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition metal salts or complexes may generally be used. Benzotriazole and/or alkylaminotriazole are particularly preferably used. Moreover, agents containing active chlorine are frequently encountered in cleaning formulations, which can significantly reduce corrosion of the silver surface. In chlorine-free cleansing products, particular use is made of oxygen-containing and nitrogen-containing organic redox-active compounds, such as dihydric and trihydric phenols, e.g. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol and derivatives of these classes of compound. Salts and complexes of inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are also frequently used. Preference is given in this context to the transition metal salts selected from the group consisting of manganese and/or cobalt salts and/or complexes, particularly preferably cobalt amine complexes, cobalt acetato complexes, cobalt carbonyl complexes, the chlorides of cobalt or of manganese, and manganese sulfate. Zinc compounds may also be used to prevent corrosion of tableware.

Redox-active substances may be added to the inventive compositions instead of, or in addition to the above described silver protection agents, e.g. the benzotriazoles. These substances are preferably inorganic redox-active substances from the group of salts and/or complexes of manganese, titanium, zirconium, hafnium, vanadium, cobalt or cerium, in which the cited metals exist in the valence states II, III, IV, V or VI.

The metal salts or complexes used should be at least partially soluble in water. Suitable counter ions for the salt formation include all usual mono, di or trivalent negatively charged inorganic anions, e.g. oxide, sulfate, nitrate, fluoride and also organic anions e.g. stearate.

In the context of the invention, metal complexes are compounds that consist of a central atom and one or a plurality of ligands as well as optionally one or a plurality of the abovementioned anions in addition. The central atom is one of the abovementioned metals in one of the abovementioned valence states. Ligands are neutral molecules or anions, which are monodentate or bidentate; in the context of the invention, the term “Ligands” is discussed in more detail in “Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart/New York, 9. Edition, 1990, page 2507”. If the charge on the central atom and the charge of the ligand(s) do not add up to zero, then according to whether a cationic or an anionic residual charge is present, either one or several of the abovementioned anions or one or more of the cations e.g. sodium, potassium, ammonium ions equalize the charge difference. Suitable complex builders are e.g. citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

The current definition for “valence state” in chemistry is given in e.g. “Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart/New York, 9th Edition, 1991, page 3168”.

Particularly preferred metal salts and/or metal complexes are selected from the group MnSO₄, Mn(II)-citrate, Mn(II)-stearate, Mn(II)-acetylacetonate, Mn(II)[1-hydroxyethane-1,1-diphosphonate], V₂O₅, V₂O₄, VO₂, TiOSO₄, K₂TiF₆, K₂ZrF₆, CoSO₄, Co(NO₃)₂, Ce(NO₃)₃ as well as their mixtures, such that preferred inventive automatic dishwasher agents are characterized in that the metal salts and/or metal complexes are selected from the group MnSO₄, Mn(II)-citrate, Mn(II)-stearate, Mn(II)-acetylacetonate, Mn(II)-[1-hydroxyethane-1,1-diphosphonate], V₂O₅, V₂O₄, VO₂, TiOSO₄, K₂TiF₆, K₂ZrF₆, CoSO₄, Co(NO₃)₂, Ce(NO₃)₃.

These metal salts and/or metal complexes are generally commercially available substances that can be incorporated into the inventive compositions for the purpose of silver corrosion protection without prior cleaning. The mixture of pentavalent and tetravalent vanadium (V₂O₅, V₂O₄, VO₂), for example, known from the SO₃ manufacturing process (Contact Process) is suitable; similarly titanyl sulfate, TiOSO₄ that is formed by diluting a solution of TiOSO₄.

The cited metal salts and/or metal complexes are comprised in the compositions according to the invention, preferably in a quantity of 0.05 to 6 wt. %, preferably 0.2 to 2.5 wt. %, based on the total weight of the composition without the container.

Glass Corrosion Inhibitors

An important criterion for rating an automatic dishwasher agent, in addition to its cleaning performance, is the visual appearance of the dried crockery after successful cleaning. Possible calcium carbonate deposits on dishes or in the inner chamber of the machine can, for example, impair customer satisfaction and thus have a causal influence on the economic success of this type of cleaning agent. A further long-standing problem with automatic dishwasher agents is the corrosion of glassware, which generally results in the occurrence of smears, streaks and scratches as well as iridescence on the glass surface. The observed effects are mainly based on two processes—firstly, the migration of alkali metal and alkaline earth metal ions out of the glass, in conjunction with a hydrolysis of the silicate lattice, and secondly in a deposition of silicate compounds onto the surface of the glass.

The cited problem can be solved with the inventive compositions, if, in addition to the abovementioned required and optional ingredients, specific glass-corrosion inhibitors are incorporated into the composition. Preferred inventive compositions therefore additionally comprise one or more magnesium and/or zinc salts and/or magnesium and/or zinc complexes.

A preferred class of compounds that can be added to the inventive agents to prevent glass corrosion are insoluble zinc salts. During the dishwasher cycle, they can attach themselves to the surface of the glass and prevent the dissolution of metal ions from the glass lattice as well as hydrolysis of the silicates. In addition, the insoluble zinc salts also prevent silicate deposits onto the glass surface and thus protect the glass from the above-mentioned consequences.

In terms of this preferred embodiment, insoluble zinc salts are zinc salts with a solubility of maximum 10 grams zinc salt per liter of water at 20° C. According to the invention, examples of particularly preferred insoluble zinc salts are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn₂(OH)₂CO₃), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn₃(PO₄)₂), and zinc pyrophosphate (Zn₂(P₂O₇)).

The cited zinc compounds are preferably used in the inventive agents in quantities that produce a content of zinc ions in the agent between 0.02 and 10 wt. %, preferably between 0.1 and 5.0 wt. % and especially between 0.2 and 1 wt. %, each based on the agent without the container. The exact content of the zinc salt or zinc salts in the agent naturally depends on the type of zinc salt—the lower the solubility of the added zinc salt, the higher must be its concentration in the inventive agents.

A further preferred class of compounds are magnesium and/or zinc salt(s) of at least one monomeric and/or polymeric organic acid. These ensure that even on repeated use, the surfaces of the glassware are not corroded, especially that no smears, streaks and scratches or iridescence occur on the glass surfaces.

Although according to the invention, any magnesium and/or zinc salt(s) of monomeric and/or polymeric organic acids can be comprised in the claimed agents, the magnesium and/or zinc salt(s) of monomeric and/or polymeric organic acids from the groups of the non-branched, saturated or unsaturated monocarboxylic acids, the branched, saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxoacids, the amino acids and/or the polymeric carboxylic acids are, however, as described above, preferred. In this group, in the context of the present invention, the following cited acids are again preferred:

The spectrum of the inventively preferred zinc salts of organic acids, preferably organic carboxylic acids, ranges from salts that are difficultly soluble or insoluble in water, i.e. with a solubility below 100 mg/L, preferably below 10 mg/L, or especially are insoluble, to such salts with solubilities in water greater than 100 mg/L, preferably over 500 mg/L, particularly preferably over 1 g/L and especially over 5 g/L (all solubilities at a water temperature of 20° C.). The first group of zinc salts includes for example zinc citrate, zinc oleate and zinc stearate, the group of soluble zinc salts includes for example zinc formate, zinc acetate, zinc lactate and zinc gluconate.

In a further preferred embodiment of the present invention, the inventive compositions comprise at least one zinc salt, however no magnesium salt of an organic acid, wherein at least one zinc salt of an organic carboxylic acid is preferred, particularly preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and/or zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

In the context of the present invention, the content of zinc salt in the preferred composition is preferably between 0.1 and 5 wt. %, preferably between 0.2 and 4 wt. % and especially between 0.4 and 3 wt. %. The content of zinc in the oxidized form (calculated as Zn²⁺) is between 0.01 and 1 wt. %, preferably between 0.02 and 0.5 wt. % and especially between 0.04 and 0.2 wt. % respectively, based on the total weight of the composition without the container.

A further subject matter of the present application is therefore a fragrance release system that comprises further active substances, in particular active substances from the group of the perfume carriers, dyes, antimicrobials, germicides, fungicides, antioxidants or corrosion inhibitors.

Bleaching Agents

In addition to the aforementioned active substances, it will be appreciated that the inventive compositions, especially compositions for use in machine dishwashers, textile washing machines or dryers, may comprise all active substances typically present in compositions for textile cleaning or dishwashing, or the care of textiles or dishes, particular preference being given to the group of the bleaching agents, bleach activators, polymers, builders, surfactants, enzymes, electrolytes, pH modifiers, fragrances, perfume carriers, dyes, hydrotropes, foam inhibitors, anti-redeposition agents, optical brighteners, graying inhibitors, shrink preventatives, anti-crease agents, color transfer inhibitors, antimicrobials, germicides, fungicides, antioxidants, corrosion inhibitors, antistats, repellent and impregnation agents, swelling and anti-slip agents, non-aqueous solvents, fabric softeners, protein hydrolyzates and UV absorbers. Such combination products are then suitable, in addition to repeated fragrancing, also for single or multiple care or cleaning of textiles or dishes.

Bleaching agents and bleach activators are important constituents of detergents or cleaning agents, and can be comprised in the inventive compositions in addition to other constituents. Among the compounds, which serve as bleaching agents and liberate H₂O₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Examples of further bleaching agents that may be employed are sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H₂O₂-liberating peracidic salts or peracids, such as perbenzoates, peroxyphthalates, diperoxyazelaic acid, phthaloimino peracid or diperoxydodecanedioic acid. Detergent tablets for machine dishwashing may also comprise bleaching agents from the group of the organic bleaches. Typical organic bleaching agents are the diacyl peroxides, such as e.g. dibenzoyl peroxide. Further typical organic bleaching agents are the peroxy acids, wherein the alkylperoxy acids and the arylperoxy acids may be named as examples. Preferred representatives that can be incorporated are (a) peroxybenzoic acid and ring-substituted derivatives thereof, such as alkyl peroxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido peroxycaproic acid, N-nonenylamido peradipic acid and N-nonenylamido persuccinates and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N,N-terephthaloyl-di(6-aminopercaproic acid).

When the inventive compositions are used as machine dishwasher detergents, then they can comprise bleach activators in order to achieve an improved bleaching action on cleaning at temperatures of 60° C. and below. Bleach activators, which can be used, are compounds which, under perhydrolysis conditions, yield aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. Substances, which carry O-acyl and/or N-acyl groups of said number of carbon atoms and/or optionally substituted benzoyl groups, are suitable. Preference is given to polyacylated alkylenediamines, in particular tetraacetyl ethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetyl glycoluril (TAGU), N-acylimides, in particular N-nonanoyl succinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or iso-nonanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In the context of the present application, further preferred added bleach activators are compounds from the group of the cationic nitriles, particularly cationic nitriles of the Formula

in which R¹ stands for —H, —CH₃, a C₁₋₂₄ alkyl or alkenyl group, a substituted C₂₋₂₄ alkyl or alkenyl group having at least one substituent from the group of —Cl, —Br, —OH, —NH₂, —CN, an alkyl or alkenylaryl group having a C₁-C₂₄-alkyl group or for a substituted alkyl or alkenylaryl group having a C₁₋₂₄ alkyl group and at least one further substituent on the aromatic ring, R² and R³, independently of one another are selected from —CH₂—CN, —CH₃, —CH₂—CH₃, —CH₂—CH₂—CH₃, —CH(CH₃)—CH₃, —CH₂—OH, —CH₂—CH₂—OH, —CH(OH)—CH₃, —CH₂—CH₂—CH₂—OH, —CH₂—CH(OH)—CH₃, —CH(OH)—CH₂—CH₃, —(CH₂CH₂—O)_(n)H with n=1, 2, 3, 4, 5 or 6 and X is an anion.

In particularly preferred agents according to the invention, there is comprised a cationic nitrile of the Formula

in which R⁴, R⁵ and R⁶ independently of one another are selected from —CH₃, —CH₂—CH₃, —CH₂—CH₂—CH₃, —CH(CH₃)—CH₃, wherein R⁴ can also be —H, and X is an anion, wherein preferably R⁵=R⁶=—CH₃ and particularly R⁴=R⁵=R⁶=—CH₃, and compounds of the formulae (CH₃)₃N⁽⁺⁾CH₂—CN X⁽⁻⁾, (CH₃CH₂)₃N⁽⁺⁾CH₂—CN X⁽⁻⁾, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂—CN X⁽⁻⁾, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂—CN X⁽⁻⁾, or (HO—CH₂—CH₂)₃N⁽⁺⁾CH₂—CN X⁽⁻⁾ are particularly preferred, wherein from the group of these substances, the cationic nitrile of formula (CH₃)₃N⁽⁺⁾CH₂—CN X⁽⁻⁾ is particularly preferred, in which X″ stands for an anion that is selected from the group chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluene sulfate (tosylate) or xylene sulfonate.

In addition to, or instead of the conventional bleach activators, so-called bleach catalysts may also be incorporated into the composition. These substances are bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen or -carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, as well as cobalt-, iron-, copper- and ruthenium-amine complexes may also be employed as the bleach catalysts.

Surfactants

In the context of the present application, preferred compositions comprise one or a plurality of surfactants from the group of anionic, non-ionic, cationic and/or amphoteric surfactants.

Preferably, one or more substances from the group of carboxylic acids, half esters of sulfuric acid and sulfonic acids, preferably from the group of fatty acids, the fatty alkyl sulfuric acids and the alkylaryl sulfonic acids are used as the acid form of anionic surfactants. In order to possess adequate surface-active properties, the cited compounds should consequently incorporate longer chain hydrocarbon radicals, i.e. there should be at least 6 carbon atoms in the alkyl or alkenyl radicals. Normally, the carbon chain distributions of the anionic surfactants are between 6 and 40, preferably 8 and 30 and especially between 12 and 22 carbon atoms.

Carboxylic acids, which find use in the form of their alkali metal salts as soaps in detergents and cleaning products, are for the most part obtained industrially from natural fats and oils by hydrolysis. While the alkaline saponification process, already used in the previous century led to the alkali salts (soaps), today industrially, only water is used to cleave the fats into glycerine and free fatty acids. Industrially practiced processes are e.g. cleavage in autoclaves or continuous high-pressure cleavage. In the context of the present invention, suitable carboxylic acids as the acid form of anionic surfactants are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid etc. In the context of the present invention, preferred fatty acids are dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) as well as the unsaturated series 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c,12c-octadecadienoic acid (linoleic acid), 9t,12t-octadecadienoic acid (linoleaidic acid) and 9c,12c,15c-octadecatrienoic acid (linolenic acid). For reasons of cost, it is preferred not to use the pure species but rather technical mixtures of the individual acids, just as they are obtained by fat cleavage. Such mixtures are, for example coconut oil fatty acid (about 6% by weight C8, 6% by weight C10, 48% by weight C12, 18% by weight C14, 10% by weight C16, 2% by weight C18, 8% by weight C18′, 1% by weight C18″), palm kernel oil fatty acid (about 4% by weight C8, 5% by weight 010, 50% by weight C12, 15% by weight C14, 7% by weight C16, 2% by weight C18, 15% by weight C18′, 1% by weight C18″), tallow fatty acid (about 3% by weight C14, 26% by weight C16, 2% by weight C16′, 2% by weight C17, 17% by weight C18, 44% by weight C18′, 3% by weight C18″, 1% by weight C18′″), hydrogenated tallow fatty acid (about 2% by weight C14, 28% by weight C16, 2% by weight C17, 63% by weight C18, 1% by weight C18′), technical-grade oleic acid (about 1% by weight C12, 3% by weight C14, 5% by weight C16, 6% by weight C16′, 1% by weight C17, 2% by weight C18, 70% by weight C18′, 10% by weight C18″, 0.5% by weight C18′″), technical-grade palmitic/stearic acid (about 1% by weight C12, 2% by weight C14, 45% by weight C16, 2% by weight C17, 47% by weight C18, 1% by weight C18′), and soybean oil fatty acid (about 2% by weight C14, 15% by weight C16, 5% by weight C18, 25% by weight C18′, 45% by weight C18″, 7% by weight C18′″).

Sulfuric acid half esters of longer chain alcohols are also anionic surfactants in their acid form and are suitable in the context of the present invention. Their alkali metal salts, particularly sodium salts, the fatty alcohol sulfates are obtained industrially from fatty alcohols, which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to afford the corresponding alkylsulfuric acids and subsequently neutralized. The fatty alcohols are thus obtained from the corresponding fatty acids or fatty acid mixtures by high pressure hydrogenation of the fatty acid methyl esters. The quantitatively most important industrial process for the manufacture of fatty alkyl sulfur acids is the sulfonation of the alcohols with SO₃/air mixtures in special cascade, falling film or multi-tube reactors.

A further class of anionic surfactant acids, which can be used according to the invention, are the alkyl ether sulfuric acids, their salts, the alkyl ether sulfates, which in comparison to the alkyl sulfates possess a higher water solubility and are less sensitive towards hard water (solubility of the Ca salts). Alkyl ether sulfur acids are synthesized, like the alkyl sulfur acids, from fatty alcohols, which are reacted with ethylene oxide to afford the corresponding fatty alcohol ethoxylates. Propylene oxide can also be used instead of ethylene oxide. The subsequent sulfonation with gaseous sulfur trioxide in short-time sulfonation reactors affords yields of over 98% of the corresponding alkyl ether sulfur acids.

In the context of the present invention, alkane sulfonic acids and olefin sulfonic acids are also suitable anionic surfactants in acid form. Alkane sulfonic acids can contain a terminal sulfonic acid group (primary alkane sulfonic acids) or one along the carbon chain (secondary alkane sulfonic acids), wherein only the secondary alkane sulfonic acids have commercial importance. They are manufactured by sulfochlorination or sulfoxidation of linear hydrocarbons. For sulfochlorination according to Reed, n-paraffins are converted with sulfur trioxide and chlorine under UV-irradiation to the corresponding sulfochlorides, which directly afford the alkane sulfonates by hydrolysis with alkalis and alkane sulfonic acids by hydrolysis with water. As the by-products from the radical reactions—di and polysulfochlorides as well as chlorinated hydrocarbons—can result from the sulfochlorination, the reaction is normally carried out with conversions of only up to 30% and then terminated.

Another manufacturing process for alkane sulfonic acids is the sulfoxidation, where n-paraffins are reacted with sulfur trioxide and oxygen under UV-irradiation. This radical reaction affords successive alkyl sulfonyl radicals, which further react with oxygen to yield alkyl persulfonyl radicals. The reaction with unreacted paraffin affords an alkyl radical and the alkyl persulfonic acid, which decomposes into an alkyl peroxysulfonyl radical and a hydroxyl radical. The reaction of both the radicals with unreacted paraffin affords the alkyl sulfonic acids and water that reacts with alkyl persulfonic acid and sulfur trioxide to sulfuric acid. In order to maintain the highest possible yield of both the end products alkyl sulfonic acid and sulfuric acid, and to suppress side reactions, this reaction is normally run with conversion rates of up to 1% and then interrupted.

Olefin sulfonates are manufactured industrially by the reaction of α-olefins with sulfur trioxide. They form zwitterion intermediates, which cyclize to so-called sultones. Under suitable conditions (alkaline or acid hydrolysis), these sultones react to form hydroxyalkane sulfonic acids or alkene sulfonic acids, both of which can also be used as anionic surfactant acids.

Alkylbenzene sulfonates have been known as powerful anionic surfactants since the nineteen thirties. At that time, alkylbenzenes were manufactured by monochlorinating Kogasin fractions and subsequent Friedel-Crafts alkylation and were sulfonated with oleum and neutralized with sodium hydroxide. For the manufacture of alkylbenzene sulfonates at the beginning of the fifties, propylene was tetramerized to branched α-dodecene and the product was converted with aluminum trichloride or hydrogen fluoride, using a Friedel-Crafts reaction, to tetrapropylbenzene that was subsequently sulfonated and neutralized. This economic possibility for manufacturing tetrapropylbenzene sulfonic acid (TPS) led to a breakthrough of this class of surfactant, which subsequently displaced the soaps as the major surfactant in detergent and cleaning products.

The inadequate biodegradability of TPS necessitated the synthesis of new alkylbenzene sulfonates, which possess an improved ecological behavior. These requirements were fulfilled by linear alkylbenzene sulfonates, which are almost the sole alkylbenzene sulfonates manufactured today and are abbreviated to ABS or LAS.

Linear alkylbenzene sulfonates are manufactured from alkylbenzenes, which are again obtained from linear olefins. For this, commercial petroleum fractions are separated into the n-paraffins of the desired purity using molecular sieves and dehydrogenated to the n-olefins, resulting in both α- as well as i-olefins. The resulting olefins, in the presence of acid catalysts and benzene, are then converted into the alkylbenzenes, wherein the choice of Friedel-Crafts catalyst has an influence on the isomer distribution of the resulting linear alkylbenzenes. By using aluminum trichloride, the content of the 2-phenyl isomers in the mixture with the 3-, 4-, 5- and other isomers, is ca. 30 wt. %; in contrast, when hydrogen fluoride is used as the catalyst, the content of 2-phenyl isomer falls below ca. 20 wt. %. Finally, today's commercial sulfonation of linear alkylbenzenes is with oleum, sulfuric acid or gaseous sulfur trioxide, the last being by far the most important. Special film or multi-tube reactors are used for the sulfonation, yielding a 97% pure alkylbenzene sulfonic acid product (ABSS), which can be used as the anionic surfactant acid in the context of the present invention.

The most varied salts, i.e. alkylbenzene sulfonates, can be obtained from the ABSS by choosing the neutralizing agent. On economic grounds, it is preferred here to manufacture and use the alkali metal salts and among them, preferably the sodium salts of the ABSS. These can be described by means of the general Formula IX:

in which the sum of x and y normally lies between 5 and 13. According to the invention, preferred anionic surfactants in acid form are C₈₋₁₆, preferably C₉₋₁₃ alkylbenzene sulfonic acids. It is further preferred in the context of the present invention to use C₈₋₁₆, preferably C₉₋₁₃ alkylbenzene sulfonic acids, which derive from alkylbenzenes that have a tetralin content below 5 wt. %, based on the alkylbenzene. It is additionally preferred to use alkylbenzene sulfonic acids, whose alkylbenzenes were manufactured by the HF-process, such that the added C₉₋₁₆, preferably C₉₋₁₃ alkylbenzene sulfonic acids have a content of 2-phenyl isomer below 22 wt. %, based on the alkylbenzene sulfonic acid.

The abovementioned anionic surfactants in their acid form can be used alone or in mixtures with one another. However, it is also possible and preferred that before the addition to the carrier material(s), additional, preferably acid ingredients of detergent and cleaning products be mixed with the anionic surfactant in acid form in quantities of 0.1 to 40 wt. %, preferably from 1 to 15 wt. % and especially from 2 to 10 wt %, each based on the weight of the mixture to be reacted.

It is also possible, of course, to add the anionic surfactant in partially or fully neutralized form. These salts can then be present in the granulation liquid as a solution, suspension or emulsion, but also as a component of the solid bed. Apart from the alkali metals (here particularly according to demand and K-salts), the cations for such anionic surfactants can be ammonium- as well as mono-, di- or triethanolalkonium-ions. Instead of mono-, di- or triethanolamine, the analogous members of mono-, di- or trimethanolamine or such alkanolamines of higher alcohols can be quaternized and used as cations.

Cationic surfactants can also be advantageously used as active substances. The cationic surfactant can be added directly as delivered into the mixer, or be sprayed, in the form of a liquid to pasty cationic surfactant preparation, onto the solid carrier material. Such cationic surfactant preparations can be prepared, for example, by mixing commercial cationic surfactants with auxiliaries such as non-ionic surfactants, polyethylene glycols or polyols. Also, lower alcohols, such as ethanol and isopropanol, can be added, wherein the amount of such lower alcohols in the liquid cationic surfactant preparation should be, on the abovementioned grounds, under 10 wt. %.

All customary materials can be considered as cationic surfactants for the inventive agent, cationic surfactants having a textile-softening effect being markedly preferred.

The inventive agents can comprise one or more cationic, textile-softening agents of Formulae X, XI or XII as cationic active substances having a textile-softening effect:

in which each group R¹, independently of one another, is chosen from C₁₋₆-alkyl, -alkenyl or -hydroxyalkyl groups; each group R², independently of one another, is chosen from C₈₋₂₈-alkyl or -alkenyl groups; R³=R¹ or (CH₂)_(n)-T-R²; R⁴=R¹ or R² or (CH₂)_(n)-T-R²; T=—CH₂—, —O—CO— or —CO—O— and n is an integer from 0 to 5.

In preferred embodiments of the present invention, the compositions comprise additional non-ionic surfactant(s) as the active substance.

Preferred non-ionic surfactants are alkoxylated, advantageously ethoxylated, particularly primary alcohols preferably containing 8 to 18 carbon atoms and, on average, 1 to 12 moles of ethylene oxide (ED) per mole of alcohol, in which the alcohol group may be linear or, preferably, methyl-branched in the 2-position or may contain e.g. linear and methyl-branched groups in the form of the mixtures typically present in oxo alcohol groups. Particularly preferred are, however, alcohol ethoxylates with linear groups from alcohols of natural origin with 12 to 18 carbon atoms, e.g. from coco-, palm-, tallow- or oleyl alcohol, and an average of 2 to 8 EO per mol alcohol. Exemplary preferred ethoxylated alcohols include C₁₂₋₁₄ alcohols with 3 EO or 4 EO, C₉₋₁₁ alcohols with 7 EO, C₁₃₋₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 ED, C₁₂₋₁₈-alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C₁₂₋₁₄ alcohol with 3 EO and C₁₂₋₁₈ alcohol with 5 EO. The cited degrees of ethoxylation constitute statistically average values that can be a whole or a fractional number for a specific product. Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE). In addition to these non-ionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Furthermore, as additional non-ionic surfactants, alkyl glycosides that satisfy the general Formula RO(G)_(x) can be added, where R means a primary linear or methyl-branched, particularly 2-methyl-branched, aliphatic group containing 8 to 22 and preferably 12 to 18 carbon atoms and G stands for a glycose unit containing 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which defines the distribution of monoglycosides and oligoglycosides, is any number between 1.0 and 10, preferably between 1.2 and 1.4.

Another class of preferred non-ionic surfactants which may be used, either as the sole non-ionic surfactant or in combination with other non-ionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters preferably containing 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.

Non-ionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallow alkyl-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The quantity in which these non-ionic surfactants are used is preferably no more than the quantity in which the ethoxylated fatty alcohols are used and, particularly no more than half that quantity.

Other suitable surfactants are polyhydroxyfatty acid amides corresponding to formula (XIII),

in which RCO stands for an aliphatic acyl group with 6 to 22 carbon atoms, R¹ for hydrogen, an alkyl or hydroxyalkyl group with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl group with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxyfatty acid amides are known substances, which may normally be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxyfatty acid amides also includes compounds corresponding to the Formula XIV,

in which R is a linear or branched alkyl or alkenyl group containing 7 to 12 carbon atoms, R¹ is a linear, branched or cyclic alkyl group or an aryl group containing 2 to 8 carbon atoms and R² is a linear, branched or cyclic alkyl group or an aryl group or an oxyalkyl group containing 1 to 8 carbon atoms, C₁₋₄ alkyl or phenyl groups being preferred, and [Z,] is a linear polyhydroxyalkyl group, of which the alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of that group.

[Z] is preferably obtained by reductive amination of a reducing sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds may then be converted into the required polyhydroxyfatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

For many applications, particularly preferred ratios of anionic surfactant(s) to non-ionic surfactant(s) are between 10:1 and 1:10, preferably between 7.5:1 and 1:5 and especially between 5:1 and 1:2. Accordingly, preferred containers according to the invention comprise the surfactant(s), preferably anionic and/or non-ionic surfactant(s) in quantities of 5 to 80 wt. %, preferably from 7.5 to 70 wt. %, particularly preferably from 10 to 60 wt. % and especially from 12.5 to 50 wt. %, each based on the weight of the enclosed solid.

As already mentioned, the use of surfactants in detergents for machine dishwashing is preferably restricted to the use of non-ionic surfactants in small amounts. Inventive compositions for machine dishwashing therefore preferably comprise only certain non-ionic surfactants, which are described below. The surfactants used in machine dishwasher detergents are typically only low-foaming non-ionic surfactants. In contrast, representatives from the groups of the anionic, cationic or amphoteric surfactants are of lesser importance. Preferred non-ionic surfactants are alkoxylated, advantageously ethoxylated, particularly primary alcohols preferably containing 8 to 18 carbon atoms and, on average, 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol group may be linear or, preferably, methyl-branched in the 2-position or may contain e.g. linear and methyl-branched groups in the form of the mixtures typically present in oxo alcohol groups. Particularly preferred are, however, alcohol ethoxylates with linear groups from alcohols of natural origin with 12 to 18 carbon atoms, e.g. from coco-, palm-, tallow- or oleyl alcohol, and an average of 2 to 8 EO per mole alcohol. Exemplary preferred ethoxylated alcohols include C₁₂₋₁₄ alcohols with 3 EO or 4EO, C₉₋₁₁ alcohol with 7 EO, C₁₃₋₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO C₁₂₋₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, as well as mixtures of C₁₂₋₁₄ alcohol with 3 EO and C₁₂₋₁₈ alcohol with 5 EO. The cited degrees of ethoxylation constitute statistically average values that can be a whole or a fractional number for a specific product. Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE). In addition to these non-ionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO 30 EO or 40 EO.

Especially in the case of detergents for machine dishwashing, it is preferred that they comprise a non-ionic surfactant with a melting point above room temperature, preferably a non-ionic surfactant having a melting point above 20° C. Preferably used non-ionic surfactants have melting points above 25° C.; particularly preferred non-ionic surfactants have melting points between 25 and 60° C., in particular between 26.6 and 43.3° C.

Suitable non-ionic surfactants with a melting and/or softening point in the cited temperature range are, for example weakly foaming non-ionic surfactants that can be solid or highly viscous at room temperature. If non-ionic surfactants are used that are highly viscous at room temperature, they preferably have a viscosity above 20 Pas, particularly preferably above 35 Pas and especially above 40 Pas. Non-ionic surfactants that have a waxy consistency at room temperature are also preferred.

Preferred non-ionic surfactants that are solid at room temperature are used and belong to the groups of alkoxylated non-ionic surfactants, more particularly ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complex surfactants, such as polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) surfactants. Such (PO/EO/PO)-non-ionic surfactants are characterized in addition as having good foam control

In one preferred embodiment of the present invention, the non-ionic surfactant with a melting point above room temperature is an ethoxylated non-ionic surfactant that results from the reaction of a monohydroxyalkanol or alkylphenol containing 6 to 20 carbon atoms with preferably at least 12 moles, particularly preferably at least 15 moles and especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol.

A particularly preferred non-ionic surfactant that is solid at room temperature is obtained from a straight-chain fatty alcohol containing 16 to 20 carbon atoms (C₁₆₋₂₀ alcohol), preferably a C₁₈ alcohol, and at least 12 moles, preferably at least 15 moles and more preferably at least 20 moles of ethylene oxide. Of these non-ionic surfactants, the so-called narrow range ethoxylates (see above) are particularly preferred.

Preferably, the room temperature solid non-ionic surfactant additionally has propylene oxide units in the molecule. These PO units preferably make up as much as 25% by weight, more preferably as much as 20% by weight and, especially up to 15% by weight of the total molecular weight of the non-ionic surfactant. Particularly preferred non-ionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which have additional polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol component of these non-ionic surfactant molecules preferably makes up more than 30 wt. %, more preferably more than 50 wt % and most preferably more than 70 wt. % of the total molecular weight of these non-ionic surfactants.

Other particularly preferred non-ionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend which contains 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylol propane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.

Non-ionic surfactants, which may be used with particular advantage, are obtainable, for example, under the name of Poly Tergent® SLF-18 from Olin Chemicals.

Another preferred surfactant may be described by the following Formula

R¹O[CH₂CH(CH₃)O]_(x)[CH₂CH₂O]_(y)[CH₂CH(OH)R²]

in which R¹ stands for a linear or branched aliphatic hydrocarbon group with 4 to 18 carbon atoms or mixtures thereof, R² means a linear or branched hydrocarbon group with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15.

Other preferred non-ionic surfactants are the end-capped poly(oxyalkylated) non-ionic surfactants corresponding to the following Formula

R¹O[CH₂CH(R³)O]_(x)[CH₂]_(k)CH(OH)[CH₂]_(j)OR²

in which R¹ and R² stand for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with 1 to 30 carbon atoms, R³ stands for H or for a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl group, x stands for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5. Each R³ in the above formula can be different for the case where x≧2. R¹ and R² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups containing 6 to 22 carbon atoms, groups containing 8 to 18 carbon atoms being particularly preferred. H, —CH₃ or —CH₂CH₃ are particularly preferred for the group R³. Particularly preferred values for x are in the range from 1 to 20 and more particularly in the range from 6 to 15.

As described above, each R³ in the above formula can be different for the case where x≧2. By this means, the alkylene oxide unit in the straight brackets can be varied. If, for example, x has a value of 3, the substituent R³ may be selected to form ethylene oxide (R³=H) or propylene oxide (R³=CH₃) units, which may be joined together in any order, for example (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for x was selected by way of example and may easily be larger, the range of variation increasing with increasing x-values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups or vice versa.

Particularly preferred end-capped poly(oxyalkylated) alcohols corresponding to the above formula have values for both k and j of 1, so that the above formula can be simplified to

R¹O[CH₂CH(R³)O]_(x)CH₂CH(OH)CH₂OR²

In this last formula, R¹, R² and R³ are as defined above and x stands for a number from 1 to 30, preferably 1 to 20 and especially 6 to 18. Surfactants in which the substituents R¹ and R² have 9 to 14 carbon atoms, R³ stands for H and x takes a value of 6 to 15 are particularly preferred.

Enzymes

To increase their washing or cleaning power, agents according to the invention can comprise enzymes, wherein in principle, any enzyme established for these purposes in the prior art may be used. These particularly include proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases as well as preferably their mixtures. In principle, these enzymes are of natural origin; improved variants based on the natural molecules are available for use in detergents and accordingly they are preferred. The agents according to the invention preferably comprise enzymes in total quantities of 1×10⁶ to 5 weight percent based on active protein. The protein concentration may be determined with the aid of known methods, for example the BCA method (bicinchonic acid; 2,2′-biquinolyl-4,4′-dicarboxylic acid) or the biuret method.

Preferred proteases are those of the subtilisin type. Examples of these are subtilisins BPN′ and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and those enzymes of the subtilises no longer however classified in the stricter sense as subtilisins thermitase, proteinase K and the proteases TW3 and TW7. Subtilisin Carlsberg in further developed form is available under the trade name Alcalase® from Novozymes AIS, Bagsværd, Denmark. Subtilisins 147 and 309 are commercialized under the trade names Esperase® and Savinase® by the Novozymes company. The variants sold under the name BLAP® are derived from the protease from Bacillus lentus DSM 5483.

Further useable proteases are, for example, those enzymes available with the trade names Durazym®, Relase®, Everlase®, Nafizym, Natalase®, Kannase® and Ovozymes® from the Novozymes Company, those under the trade names Purafect®, Purafect® OxP and Properase® from Genencor, that under the trade name Protosol® from Advanced Biochemicals Ltd., Thane, India, that under the trade name Wuxi® from Wuxi Snyder Bioproducts Ltd., China, those under the trade names Proleather® and Protease P® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and that under the designation Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of further useable amylases according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens and from B. stearothermophilus, as well as their improved further developments for use in detergents and cleaning agents. The enzyme from B. licheniformis is available from the Novozymes Company under the name Termamyl® and from the Genencor Company under the name Purastar(ST. Further development products of this α-amylase are available from the Novozymes Company under the trade names Duramyl® and Termamyl® ultra, from the Genencor Company under the name Purastar® OxAm and from Daiwa Seiko Inc., Tokyo, Japan as Keistase®. The α-amylase from B. amyloliquefaciens is commercialized by the Novozymes Company under the name BAN®, and derived variants from the α-amylase from B. stearothermophilus under the names BSG® and Novamyl® also from the Novozymes Company.

Moreover, for these purposes, attention should be drawn to the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrine-glucanotransferase (CGTase) from B. agaradherens (DSM 9948); likewise the fusion products of the cited molecules can be used.

Moreover, further developments of α-amylase from Aspergillus niger and A. oryzae available from the Company Novozymes under the trade name Fungamyl® are suitable. A further commercial product is the amylase-LT® for example.

The agents according to the invention can comprise lipases or cutinases, particularly due to their triglyceride cleaving activities, but also in order to produce in situ peracids from suitable preliminary steps. These include the available or further developed lipases originating from Humicola lanuginosa (Thermomyces lanuginosus), particularly those with the amino acid substitution D96L. They are commercialized, for example by the Novozymes Company under the trade names Lipolase®, Lipolase® Ultra, LipoPrime®, Lipozyme® and Lipex®. Moreover, suitable cutinases, for example are those that were originally isolated from Fusarium solani pisi and Humicola insolens, Likewise useable lipases are available from the Amano Company under the designations Lipase CEO, Lipase P®, Lipase B®, and Lipase CES®, Lipase AKG®, Bacillis sp. Lipase®, Lipase AP®, Lipase M-AP® and Lipase AML®. Suitable lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii are for example available from Genencor Company. Further important commercial products that may be mentioned are the commercial preparations M1 Lipase® and Lipomax® originally from Gist-Brocades Company, and the commercial enzymes from the Meito Sangyo KK Company, Japan under the names Lipase MY-30®, Lipase OF® and Lipase PL® as well as the product Lumafast® from Genencor Company.

Agents according to the invention, particularly when they are destined for treating textiles, can comprise cellulases, according to their purpose, as pure enzymes, as enzyme preparations, or in the form of mixtures, in which the individual components advantageously complement their various performances. Among these aspects of performance are particular contributions to primary washing performance, to secondary washing performance of the product, (anti-redeposition activity or inhibition of graying) and softening or brightening (effect on the textile), through to practicing a “stone washed” effect.

A usable, fungal endoglucanase(EG)-rich cellulase preparation, or its further developments are offered by the Novozymes Company under the trade name Celluzyme®. The products Endolase® and Carezyme® based on the 50 kD-EG, respectively 43 kD-EG from H. insolens DSM 1800 are also obtainable from the Novozymes Company. Further possible commercial products from this company are Cellusoft® and Renozyme®. It is equally possible to use the Melanocarpus 20 kD EG cellulase, which is available under the trade names Ecostone® and Biotouch® from AB Enzymes, Finland. Further commercial products from the AB Enzymes Company are Econase® and Ecopulp®. A further suitable cellulase from Bacillus sp. CBS 670.93 is available under the trade name Puradex® from Genencor. Other commercial products from Genencor are Genencor detergent cellulase L and IndiAge® Neutra.

The agents according to the invention can comprise additional enzymes, which are summarized under the term hemicellulases. These include, for example mannanases, xanthanlyases, pectinlyases (=pectinases), pectinesterases, pectatlyases, xyloglucanases (=xylanases), pullulanases and β-glucanases. Suitable mannanases, for example are available under the names Gamanase® and Pektinex AR® from Novozymes Company, under the names Rohapec® B1 from AB Enzymes and under the names Pyrolase® from Diversa Corp., San Diego, Calif., USA. β-Glucanase, extracted from B. subtilis, is available under the name Cereflo® from the Novozymes Company.

To increase the bleaching action, the detergents or cleaning agents according to the invention can comprise oxidoreductases, for example oxidases, oxygenases, katalases, peroxidases, like halo-, chloro-, bromo-, lignin-, glucose- or manganese-peroxidases, dioxygenases or laccases (phenoloxidases, polyphenoloxidases). Suitable commercial products are Denilite® 1 and 2 from the Novozymes Company. Advantageously, additional, preferably organic, particularly preferably aromatic compounds are added that interact with the enzymes to enhance the activity of the relative oxidoreductases or to facilitate the electron flow (mediators) between the oxidizing enzymes and the stains over strongly different redox potentials.

The enzymes used in the inventive agents either stem originally from microorganisms, such as the species Bacillus, Streptomyces, Humicola, or Pseudomonas, and/or are produced according to known biotechnological processes using suitable microorganisms such as by transgenic expression hosts of the species Bacillus or filamentary fungi.

Purification of the relevant enzymes follows conveniently using established processes such as precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, mixing with chemicals, deodorization or suitable combinations of these steps.

The enzymes can be added to the inventive agents in each established form according to the prior art. Included here, for example, are solid preparations obtained by granulation, extrusion or lyophilization, or particularly for liquid agents or agents in the form of gels, enzyme solutions, advantageously highly concentrated, of low moisture content and/or mixed with stabilizers.

As an alternative application form, the enzymes can also be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzyme is embedded in a solidified gel, or in those of the core-shell type, in which an enzyme-containing core is covered with a water-, air- and/or chemical-impervious protective layer. Further active principles, for example stabilizers, emulsifiers, pigments, bleaches or colorants can be applied in additional layers. Such capsules are made using known methods, for example by vibratory granulation or roll compaction or by fluid bed processes. Advantageously, these types of granulates, for example with an applied polymeric film former, are dust-free and as a result of the coating are storage stable.

In addition, it is possible to formulate two or more enzymes together, so that a single granulate exhibits a plurality of enzymatic activities.

A protein and/or enzyme in an inventive agent can be protected, particularly in storage, against deterioration such as, for example inactivation, denaturation or decomposition, for example through physical influences, oxidation or proteolytic cleavage. An inhibition of the proteolysis is particularly preferred during microbial preparation of proteins and/or enzymes, particularly when the compositions also contain proteases. For this use, inventive agents can comprise stabilizers; the supply of these types of agents represents a preferred embodiment of the present invention.

One group of stabilizers are the reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives containing aromatic groups, for example ortho, meta or para substituted phenyl boronic acids or their salts or esters. Peptide aldehydes, i.e. oligopeptides with reduced C-terminus are also suitable. Ovomucoid and leupeptin, inter alia, are mentioned as peptidic protease inhibitors; an additional option is the formation of fusion proteins from proteases and peptide inhibitors.

Further enzyme stabilizers are amino alcohols like mono-, di-, tri-ethanolamine and -propanolamine and their mixtures, aliphatic carboxylic acids up to C₁₂, such as, for example succinic acid, other dicarboxylic acids or salts of the cited acids. End capped alkoxylated fatty acid amides are also suitable as stabilizers.

Lower aliphatic alcohols, but above all polyols such as, for example glycerine, ethylene glycol, propylene glycol or sorbitol are further frequently used enzyme stabilizers. Di-glycerol phosphate also protects against denaturation by physical influences. Likewise, calcium salts are used, such as, for example calcium acetate or calcium formate, and magnesium salts.

Polyamide oligomers or polymeric compounds like lignin, water-soluble vinyl copolymers or, like cellulose ethers, acrylic polymers and/or polyamides stabilize the enzyme preparations against inter alia physical influences or pH variations. Polymers containing polyamine-N-oxide act simultaneously as enzyme stabilizers and color transfer inhibitors. Other polymeric stabilizers are the linear C₈-C₁₈ polyoxyalkylenes. Alkyl polyglycosides can stabilize the enzymatic components of the inventive agents and even increase their performance. Crosslinked nitrogen-containing compounds fulfill a dual function as soil release agents and as enzyme stabilizers.

Reducing agents and antioxidants such as sodium sulfite or reducing sugars increase the stability of enzymes against oxidative decomposition.

The use of combinations of stabilizers is preferred, for example of polyols, boric acid and/or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamine compounds and with reducing salts. The effect of peptide-aldehyde stabilizers can be increased by the combination with boric acid and/or boric acid derivatives and polyols and still more by the additional use of divalent cations, such as for example calcium ions.

In the context of the present invention, the use of liquid enzyme formulations is particularly preferred. Preferred inventive compositions additionally comprise enzymes and/or enzyme preparations, preferably solid and/or liquid protease preparations and/or amylase preparations in quantities from 1 to 5 wt. %, preferably from 1.5 to 4.5 wt. % and in particular from 2 to 4 wt. %, each based on the total composition.

A large number of the most varied salts from the group of the inorganic salts can be employed as the electrolytes. Preferred cations are the alkali metal and alkaline earth metals, preferred anions are the halides and sulfates. The addition of NaCl or MgCl₂ to the inventive granulates is preferred from the industrial manufacturing point of view.

LIST OF REFERENCE NUMERALS

-   1 closure -   2 closure cap -   3 outer surface -   4 receiving opening for portion storage -   5 dosing volume -   6 screw thread -   7 portion storage -   8 substance -   9 weakened opening -   10 screw thread -   11 container -   12 portion volume -   13 portion closure -   14 plug -   15 portion opening -   16 seal -   17 portion opening

The invention is described in more detail using the examples that are illustrated in the following Figures. The drawings show:

FIG. 1: closure with receiving opening for portion storage in cross section

FIG. 2: closure with receiving openings for portion storage in top view

FIG. 3: closure with receiving openings for portion storage in top view

FIG. 4: portion storage with closure

FIG. 5: portion storage with plug

FIG. 6: portion storage with sealed openings

FIG. 7: portion storage with non-free flowing substance

FIG. 8: closure with portion storage with non-free flowing substance in cross section

DESCRIPTION OF THE FIGURES

A cross sectional view of the inventive closure 1 is shown in FIG. 1. The closure 1 has an outer surface 3 and a closure cap 2 extending over one front end of the outer surface 3, thus forming a beaker-like dosing volume 5 of the closure 1.

The closure 1 has a plurality of receiving openings 4 for portion storage 7. A receiving opening 4 cooperates with a portion storage 7 such that the portion storage 7 is detachably fixed in the receiving opening 4. This can be realized, for example, by means of a form closure, frictional connection or adhesive bond between the portion storage 7 and the receiving opening 4. The fixation is appropriately configured such that the portion storage 7 cannot involuntarily fall out of the receiving opening e.g. during transportation or storage.

In a preferred embodiment of the invention, the portion storage 7 is fixed in a receiving opening 4 by means of a removable press fit. In a further preferred variant of the embodiment, the fixation between portion storage 7 and receiving opening 4 is ensured by a removable snap-in connection.

The closure 1 has an internal thread that corresponds with an external thread molded on the container 11, thereby allowing a preferably liquid-tight closing of the container 11 by the closure 1.

A top view of the closure 1 with receiving openings 4 for portion storage 7 is shown in FIG. 2. Here, a plurality of receiving openings 4 is arranged concentrically around the central point of the closure 1. The receiving openings 4 can be designed as a through-going bore or as a blind hole. According to the embodiment shown in FIG. 2, a receiving opening 4 is completely enclosed by the closure 1.

A further embodiment of the closure according to the invention is shown in FIG. 3, in which the receiving openings 4 are only partially enclosed by the closure 1 such that clip-like openings are formed, into which a portion storage 7 can be fixed.

FIG. 4 shows a portion storage 7 with a closure 13 that tightly seals the portion volume 12 from the environment. The closure 13 is advantageously designed in such a way that the portion volume 12 can form a liquid-tight seal to the environment. The closure 13 is particularly preferably designed in such a way that the portion volume 12 can be closed to form an essentially tight seal against the emission of fragrances.

The closure 13 is removably arranged on the portion storage 7 through a form closure, frictional connection or adhesive bond. In particular, the portion volume 12 can be tightly sealed against the environment by the closure 13 using a press fit, a screw closure, or an adhesive.

FIG. 5 shows a portion storage 7, in which the portion volume 12 is sealed up with a plug 14. The plug 14 preferably made of an elastic material and is designed in such a way that the portion volume 12 is sealed at least liquid-tight.

A portion storage 7 with sealed openings 15 is illustrated in FIG. 6. The openings 15 can be configured as bores through the outer surface, bottom and/or top surfaces of the portion storage 7. However, any other suitable shape is also conceivable for the openings 15, such as for example slits, grills etc.

The seal 16 of the opening 15 is designed such that the openings 15 are sealed liquid-tight. In a particularly preferred embodiment, the seal is essentially sealed tight against the emission of fragrances from the portion volume 12 into the environment.

The sealing can especially concern a plastic film that is at least partially, preferably removably sealed to the surface of the portion storage 7. It is also conceivable to seal up the openings 15 with a sleeve, wherein a suitable plastic film is pulled tightly around the portion storage.

As is illustrated in FIG. 7, the portion storage 7 is then also filled with a non-free flowing substance 8. In this case the portion storage 7 can be molded like a beaker that possesses an open top end 17.

Alternatively, the portion storage can also have openings 15 on the outer surface.

In this context, non-free flowing means that the substance 8 inside the portion volume 12 cannot escape through the openings 15,17 into the surroundings. This can be achieved, for example by using a solid or solid granules, wherein the solid granule, for example, is dimensioned such that it does not pass through the openings 15,17 or the solid is fixed in the portion volume.

The use of the portion storage 7 disclosed in FIG. 7 is shown in a closure 1 according to the invention in FIG. 8. The portion storages 7 can be arranged in two places in the closure 1. In a first closure position, the openings 17 of the portion storage are completely sealed by the outer or bottom surface of the receiving opening.

On removing the portion storage 7 from the receiving opening 4, the portion storage 7 can be arranged in a second position in a receiving opening 4 of the closure 1, in which the opening 17 of the portion storage 7 communicates with the environment and components of the substance 8 present in the portion storage 7 are released, preferably by diffusion, into the surroundings.

In addition, in this case, the opening or openings of the portion storage 7 can be covered with a protective film that initially prevents any release of product by diffusion into the surroundings. The protective film can be ripped off, for example, or rubbed off, such that the product 8 can then be released into the surroundings. 

1-11. (canceled)
 12. A closure (1) for a container, particularly for granular or free-flowing products, comprising: a closure cap (2) with an outer surface (3) that is at least partially joined to the closure cap (2) and fastening means (6) that cooperate with the container so that a disbursement opening of the container can be sealed by the closure (1), and a plurality of portion storages (7) that are at least partially filled with at least one substance selected from the group consisting of fragrances, dyes and surfactants, wherein the closure (1) has one or more receiving openings (4) to receive the plurality of portion storages (7).
 13. The closure (1) according to claim 12, wherein an essentially form locked, material joined and/or friction locked connection exists between the receiving openings (4) and the portion storages (7).
 14. The closure (1) according to claim 12, wherein the portion storages (7) are removably arranged in the receiving openings (4).
 15. The closure (1) according to claim 12, wherein a force of at least 0.1 N is required to release one portion storage (7) from its associated receiving opening (4).
 16. The closure (1) according to claim 12, wherein the receiving openings (4) for receiving the portion storages (7) are blind bores.
 17. The closure (1) according to claim 12, wherein the portion storages (7) include predetermined break points.
 18. The closure (1) according to claim 12, wherein the portion storages (7) have an opening (15, 17) that can be sealed with a sealing means (16).
 19. The closure (1) according to claim 12, wherein each portion storage (7) holds a different substance (8) or a different mixture of substances (8) or additives.
 20. The closure (1) according to claim 12, wherein at least one portion storage (7) holds a substance (8) that comprises more than 1 wt. % of fragrance(s).
 21. The closure (1) according to claim 12, wherein at least one portion storage (7) has at least one opening that cooperates with the receiving opening (4) for receiving the portion storage (7) such that the opening (17) of the portion storage (7) fixed in the closure (1) is sealed.
 22. The closure (1) according to claim 12, wherein at least one of the portion storages (7) contains a non-free flowing substance (8).
 23. A container closure, comprising: a cap having fastening means to removably attach the cap to a container for a free-flowing product, said cap defining a dosing volume and having one or more receiving openings; and at least one portion storage defining an internal volume to hold at least one substance, and said portion storage is removably held in one receiving opening.
 24. The container closure of claim 23, wherein the portion storage is at least partially filled with at least one substance selected from the group consisting of fragrances, dyes and surfactants.
 25. The container closure of claim 23, wherein a plurality of portion storages are held in the cap, with each portion storage held within a respective one receiving opening.
 26. The container closure of claim 25, wherein each portion storage holds a different substance or a different mixture of substances or additives.
 27. The container closure of claim 26, wherein an essentially form locked, material joined and/or friction locked connection exists between the receiving openings and the portion storages.
 28. The container closure of claim 23, where the at least one portion storage has at least one opening that cooperates with the receiving opening for receiving the portion storage such that the opening of the portion storage is sealed when the portion storage is held in the receiving opening.
 29. The container closure of claim 23, wherein the container has a neck and the fastening means cooperate with said neck.
 30. The container closure of claim 23, wherein the free flowing product is a liquid or granular product. 